US9783657B2 - Renewable and cost-effective fillers for polymeric materials - Google Patents

Renewable and cost-effective fillers for polymeric materials Download PDF

Info

Publication number
US9783657B2
US9783657B2 US13/784,055 US201313784055A US9783657B2 US 9783657 B2 US9783657 B2 US 9783657B2 US 201313784055 A US201313784055 A US 201313784055A US 9783657 B2 US9783657 B2 US 9783657B2
Authority
US
United States
Prior art keywords
polymer
composition
composites
particulate
date
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US13/784,055
Other versions
US20130178562A1 (en
Inventor
Fares D. ALSEWAILEM
Yazeed A. BINKHEDER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
King Abdulaziz City for Science and Technology KACST
Original Assignee
King Abdulaziz City for Science and Technology KACST
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by King Abdulaziz City for Science and Technology KACST filed Critical King Abdulaziz City for Science and Technology KACST
Priority to US13/784,055 priority Critical patent/US9783657B2/en
Assigned to KING ABDULAZIZ CITY FOR SCIENCE AND TECHNOLOGY reassignment KING ABDULAZIZ CITY FOR SCIENCE AND TECHNOLOGY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ALSEWAILEM, FARES D., BINKHEDER, YAZEED A.
Publication of US20130178562A1 publication Critical patent/US20130178562A1/en
Application granted granted Critical
Publication of US9783657B2 publication Critical patent/US9783657B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L99/00—Compositions of natural macromolecular compounds or of derivatives thereof not provided for in groups C08L89/00 - C08L97/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape

Definitions

  • thermoplastic matrices and bio-fillers have been reported in the literature, wherein various bio-fillers, such as wheat straw, corncob, rice husk, and sugarcane bagasse were incorporated with polymer matrices, such as polypropylene, high-density polyethylene (HDPE), low-density polyethylene, and polyvinyl chloride. From an economic point of view, incorporating a cost-effective filler in a polymer will only be feasible if it does not drastically alter the main matrix-resin characteristics, such as mechanical properties.
  • polymer matrices such as polypropylene, high-density polyethylene (HDPE), low-density polyethylene, and polyvinyl chloride.
  • date pits On the consumption of date fruit as a main daily meal in almost each Saudi dwelling, date pits are usually discarded as materials with no use or value. Nevertheless, these presumably designated waste materials, i.e., date pits, contain important constituents such as oils (up to 10%), minerals (considerably rich in potassium), and fibers (46.4%) that may be utilized for specific purposes.
  • Ghazanfari et al. (“Thermal and Mechanical Properties of Blends and Composites from HDPE and Date Pits Particles”, Journal of Composite Materials, 42(1) (2008); pp. 77-89) disclose formulating polymer-date pits composites based on HDPE as the hosting polymer, and conclude that incorporating date pit flour with HDPE tends to decrease the melt flow index (MFI), and at the same time increase the thermal conductivity of the resulting composites.
  • the date pits investigated by Ghazanfari et al. are of the Abdoulahi cultivar, which demonstrate reductions in tensile strength as compared to non-composited (neat) polymer, on increasing weight percentages of date pit flour in the composites.
  • FIGS. 1( a )-( c ) show scanning electron micrographs of melt fracture surfaces of various loadings of date pit particulate in high density polyethylene matrices
  • FIG. 4 shows a graph comparing the Tensile Strengths of various date pit particulate/high density polyethylene composites at various particulate loading levels.
  • the melt processing according to the present invention can be practiced with a number of different thermoplastic polymers to form the composite matrix, such as those selected from the group consisting of polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polymethylmethacrylate, polycarbonate, acrylonitrile-butadiene-styrene (ABS) and polyamide.
  • thermoplastic polymers such as those selected from the group consisting of polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polymethylmethacrylate, polycarbonate, acrylonitrile-butadiene-styrene (ABS) and polyamide.
  • ABS acrylonitrile-butadiene-styrene
  • FIG. 1 shows the morphology of the fractured surface of the blends. It is clearly seen that some fibril morphology has developed. As far the mechanical properties, compounding polymer with date pits particulate did not affect important properties such as tensile strength (ASTM D-638), even at relatively high filler content, e.g 40 wt % ( FIG. 4 ).
  • Toughness modifiers were added to the composites to compensate for the reduction in some properties, such as impact strength using some melated polyolefins elastomers (e.g. ethyelene/propylene grafted with maleic anhydride, indicated as EP-g-MA).
  • FIG. 3( b ) shows the morphology of melt fracture surface of a composite containing 30 wt % K and 70 wt % PS.

Abstract

Polymer composites are provided, and more particularly, polymer composites of ground date pits disposed in a polymer matrix. The composites can be formed by a process of preparing reinforced polymer composites having a fibril melt fracture surface, including blending a mixture of date pit particulate with a thermoplastic polymer; melting the mixture; and forcing the melt through a die to produce the polymer composite having a fibril containing surface.

Description

CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of U.S. application Ser. No. 13/275,977, filed on Oct. 18, 2011, the contents of which are incorporated by reference in their entirety herein.
FIELD OF THE INVENTION
The invention relates to a polymer composite, and more particularly, to a polymer composite of ground date pits disposed in a polymer matrix.
BACKGROUND OF THE INVENTION
Fillers are routinely used by polymer and plastic industry to reduce the cost of end products and to enhance some desired properties, such as physical and mechanical properties. However, conventional filler materials can be costly and therefore need to be processed in an efficient manner, and conventional inorganic fillers, such as aluminium trihydroxide and the like may pose environment risks when used as polymer fillers.
Formulation of biocomposites has been an attractive endeavor for researchers in the last decade. There are several advantages, either environmental or economical, of using biocomposites over ordinary composites, especially those based on thermoplastics matrices, for various applications such as structural and food packaging. The biodegradability feature of such composites offers a solution for the problem of municipal waste management. Besides the biodegradability of polymers filled with biomaterials, the availability of these fillers, normally of agricultural residue origin, at very low cost levels makes the production of these composites economically feasible.
Several biocomposite systems of thermoplastic matrices and bio-fillers have been reported in the literature, wherein various bio-fillers, such as wheat straw, corncob, rice husk, and sugarcane bagasse were incorporated with polymer matrices, such as polypropylene, high-density polyethylene (HDPE), low-density polyethylene, and polyvinyl chloride. From an economic point of view, incorporating a cost-effective filler in a polymer will only be feasible if it does not drastically alter the main matrix-resin characteristics, such as mechanical properties.
Saudi Arabia is well recognized for its palm trees (Phoenix dactylifera L.). In addition, Saudi Arabia is among the largest world producers of date fruit, 4700,000 MT per year. On the consumption of date fruit as a main daily meal in almost each Saudi dwelling, date pits are usually discarded as materials with no use or value. Nevertheless, these presumably designated waste materials, i.e., date pits, contain important constituents such as oils (up to 10%), minerals (considerably rich in potassium), and fibers (46.4%) that may be utilized for specific purposes.
Ghazanfari et al. (“Thermal and Mechanical Properties of Blends and Composites from HDPE and Date Pits Particles”, Journal of Composite Materials, 42(1) (2008); pp. 77-89) disclose formulating polymer-date pits composites based on HDPE as the hosting polymer, and conclude that incorporating date pit flour with HDPE tends to decrease the melt flow index (MFI), and at the same time increase the thermal conductivity of the resulting composites. The date pits investigated by Ghazanfari et al. are of the Abdoulahi cultivar, which demonstrate reductions in tensile strength as compared to non-composited (neat) polymer, on increasing weight percentages of date pit flour in the composites.
U.S. Pat. No. 4,011,130 to Worden discloses waterlaid sheets comprising essential solids consisting of (I) elastomeric (polyurethane) binder, and (II) nonelastomeric solids comprising inflexible, non-fibrous, rounded, particulate fillers (which may be vegetable flours prepared from peach pits, apricot pits and cherry pits) and a fibrous reinforcing component. The waterlaid sheets are useful as substitutes for leather in the manufacture of footwear, particularly as the outsole or insole portion of a shoe. However, no comparison of tensile strength between the neat polymer and the polymer composite is provided.
Accordingly, polymer and plastic industries would benefit from a demonstration of affordable, efficient bio-fillers which would reduce the cost of the final products and yet not diminish the strength characteristics of the polymer, as compared to the corresponding non-composited polymer.
SUMMARY OF THE INVENTION
In a first aspect of the invention, a process of preparing a reinforced polymer composite having a fibril melt fracture surface, comprises blending a mixture of date pit particulate with a thermoplastic polymer; melting the mixture; and forcing the melt through a die to produce the polymer composite having a fibril containing surface.
In another aspect the invention, composition comprises a mixture of date pit particulate from the fruit of Phoenix dactylifera L., variety khlaas or sekari, and a thermosetting polymer selected from the group consisting of epoxies, vinyl esters and polyesters.
In yet another aspect of the invention, a process of preparing a reinforced polymer composite, comprises solution blending a mixture of date pit particulate from the fruit of Phoenix dactylifera L., variety khlaas or sekari, and a solution of a thermosetting polymer, and removing solvent from the solution.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is described in the detailed description which follows, in reference to the noted plurality of drawings by way of non-limiting examples of exemplary embodiments of the present invention.
FIGS. 1(a)-(c) show scanning electron micrographs of melt fracture surfaces of various loadings of date pit particulate in high density polyethylene matrices;
FIGS. 2(a) and (b) show scanning electron micrographs of melt fracture surfaces of various loadings of date pit particulate in polystyrene matrices;
FIGS. 3(a) and (b) show scanning electron micrographs of melt fracture surfaces of composites of polystyrene, date pit particulates and two different compounding modifiers; and
FIG. 4 shows a graph comparing the Tensile Strengths of various date pit particulate/high density polyethylene composites at various particulate loading levels.
 DETAILED DESCRIPTION OF THE INVENTION
The invention relates to composites of polymers filled with naturally occurring fillers. More specifically, it has been found that the fruit of dates, i.e. the date pits, can be ground into particulate and blended with polymers to form composites having unique surface characteristics upon melt processing of the composites, without sacrificing the overall strength characteristics of the polymers, as compared to the corresponding non-composited polymers.
Advantageously, the processes and products of the present invention provide inexpensive, renewable sources for polymer fillers which can act to reduce the overall cost of polymeric articles made from the composites, but also provide an avenue for reducing waste from the consumption of dates, commonly an every-day occurrence in many Middle Eastern households.
In implementing the present invention a mixture of date pit particulate can be blended with a thermoplastic polymer, the mixture melted, in for example a melt extruder as is known in the art, and the melt is forced through an extrusion die to produce a polymer composite having a fibril containing surface. Upon examination of the surface using scanning electron microscopy (SEM), it is found that the surface of the melt processed composites demonstrate a unique, fibril-containing melt fracture surface, which can enhance physical characteristics of the extruded polymer compositions, such as toughness and stiffness, as compared to neat polymers.
In embodiments, the date pit particulate can be particulate from the fruit of Phoenix dactylifera L., variety khlaas or sekari, which varieties are commonly consumed in large quantities in Middle Eastern households, such as in Saudi Arabia. The date pits are advantageously ground or chopped to particulate of an average size of between about 0.25 mm and 1.0 mm.
The melt processing according to the present invention can be practiced with a number of different thermoplastic polymers to form the composite matrix, such as those selected from the group consisting of polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polymethylmethacrylate, polycarbonate, acrylonitrile-butadiene-styrene (ABS) and polyamide. Those skilled in the art will recognize that many other such thermoplastic polymers can be melt processed into date pit particulate/polymer composites and articles, such as molded articles, according to the present invention.
The concentration or loading of the date pit particulate in the composite is not particularly limited, and can advantageously be in an amount of between about 1 and about 40 wt % based on the weight of the composite. For example when the polymer is high density polyethylene, the composite can contain from 5 wt % to 30 wt % of date pit particulate from the variety sekari; or from 10 wt % to 40 wt % of date pit particulate from the variety khlaas. When the polymer is polystyrene, the composite can contain from 10 wt % to 40 wt % of date pit particulate from the variety khlaas, or from 5 wt % to 30 wt % of date pit particulate from the variety sekari.
In any event, the polymer composite demonstrates Tensile Strength varying no more than about 10% from that of the uncomposited polymer. Unexpectedly, date pit particulate/polymer composites can be successfully produced from thermosetting polymers too, such as from the group consisting of epoxies, vinyl esters and polyesters.
In this embodiment, a reinforced polymer composite is formed by solution blending a mixture of date pit particulate from the fruit of Phoenix dactylifera L., variety khlaas or sekari, and a solution of a thermosetting polymer, and removing solvent from the solution. Particulate loadings can advantageously be from about 5 wt % to about 40 wt %, depending on the date pit particulate/polymer combination.
EXAMPLES Example 1 High Density Polyethylene (HDPE)/sekari (S) Composites
Composites were formulated by melt extrusion where 10 to 40 wt % of date pit particulate was dispersed in a polymer matrix (HDPE). FIG. 1 shows the morphology of the fractured surface of the blends. It is clearly seen that some fibril morphology has developed. As far the mechanical properties, compounding polymer with date pits particulate did not affect important properties such as tensile strength (ASTM D-638), even at relatively high filler content, e.g 40 wt % (FIG. 4).
Example 2 Polystyrene (PS)/Date Pit Composites
Samples of PS/date pit particulate composites were prepared and the morphology of the blends' melt fracture surfaces was studied by scanning electron microscope (SEM). FIG. 2 shows the morphology of PS/date pit particulates at 30 wt % particulate loading. The morphology exhibited some fibril-like characteristics, and satisfactory adhesion between date pit particulates and polymer matrix.
Example 3 Coupling Agent Composites
Coupling agents and compatibilizers such as isocynate, silane, and di-phenylmethane were compounded with the polymer/date pit particulate composites to enhance the surface morphology. FIG. 3(a) shows effect of adding di-phenylmethane (DPHM) to the melt fracture surface morphology of the composite containing 30 wt % K and 70 wt % PS.
Example 4 Toughness Modifier Composites
Toughness modifiers were added to the composites to compensate for the reduction in some properties, such as impact strength using some melated polyolefins elastomers (e.g. ethyelene/propylene grafted with maleic anhydride, indicated as EP-g-MA). FIG. 3(b) shows the morphology of melt fracture surface of a composite containing 30 wt % K and 70 wt % PS.
The foregoing examples have been provided for the purpose of explanation and should not be construed as limiting the present invention. While the present invention has been described with reference to an exemplary embodiment, Changes may be made, within the purview of the appended claims, without departing from the scope and spirit of the present invention in its aspects. Also, although the present invention has been described herein with reference to particular materials and embodiments, the present invention is not intended to be limited to the particulars disclosed herein; rather, the present invention extends to all functionally equivalent structures, methods and uses, such as are within the scope of the appended claims.

Claims (7)

What is claimed:
1. A composition comprising a mixture of date pit particulate from the fruit of Phoenix dactylifera L., variety khlaas or sekari, and a thermosetting polymer selected from the group consisting of epoxies, vinyl esters and polyesters, wherein the date pit particulate has an average size of between about 0.25 mm and 1.0 mm.
2. The composition of claim 1, wherein the date pit particulate is present in an amount of between about 1 and about 40 wt % based on the total weight of the composition.
3. The composition of claim 1, wherein the composition demonstrates tensile strength varying no more than about 10% from that of the uncomposited polymer.
4. The composition of claim 1, further comprising from 5 wt % to 30 wt % of date pit particulate from the fruit of Phoenix dactylifera L., variety sekari based on the total weight of the composition.
5. The composition of claim 4, wherein the composition demonstrates tensile strength varying no more than about 10% from that of the uncomposited polymer.
6. The composition of claim 1, further comprising from 10 wt % to 40 wt % of date pit particulate from the fruit of Phoenix dactylifera L., variety khlaas based on the total weight of the composition.
7. The composition of claim 6, wherein the composition demonstrates tensile strength varying no more than about 10% from that of the uncomposited polymer.
US13/784,055 2011-10-18 2013-03-04 Renewable and cost-effective fillers for polymeric materials Active 2034-04-11 US9783657B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/784,055 US9783657B2 (en) 2011-10-18 2013-03-04 Renewable and cost-effective fillers for polymeric materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/275,977 US9902842B2 (en) 2011-10-18 2011-10-18 Renewable and cost-effective fillers for polymeric materials
US13/784,055 US9783657B2 (en) 2011-10-18 2013-03-04 Renewable and cost-effective fillers for polymeric materials

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US13/275,977 Division US9902842B2 (en) 2011-10-18 2011-10-18 Renewable and cost-effective fillers for polymeric materials

Publications (2)

Publication Number Publication Date
US20130178562A1 US20130178562A1 (en) 2013-07-11
US9783657B2 true US9783657B2 (en) 2017-10-10

Family

ID=48086401

Family Applications (6)

Application Number Title Priority Date Filing Date
US13/275,977 Active 2033-11-22 US9902842B2 (en) 2011-10-18 2011-10-18 Renewable and cost-effective fillers for polymeric materials
US13/784,067 Active US8664300B2 (en) 2011-10-18 2013-03-04 Renewable and cost-effective fillers for polymeric materials
US13/784,055 Active 2034-04-11 US9783657B2 (en) 2011-10-18 2013-03-04 Renewable and cost-effective fillers for polymeric materials
US15/870,401 Active 2031-12-07 US10557020B2 (en) 2011-10-18 2018-01-12 Renewable and cost-effective fillers for polymeric materials
US16/438,874 Abandoned US20190292353A1 (en) 2011-10-18 2019-06-12 Renewable and cost-effective fillers for polymeric materials
US16/438,887 Abandoned US20190292354A1 (en) 2011-10-18 2019-06-12 Renewable and cost-effective fillers for polymeric materials

Family Applications Before (2)

Application Number Title Priority Date Filing Date
US13/275,977 Active 2033-11-22 US9902842B2 (en) 2011-10-18 2011-10-18 Renewable and cost-effective fillers for polymeric materials
US13/784,067 Active US8664300B2 (en) 2011-10-18 2013-03-04 Renewable and cost-effective fillers for polymeric materials

Family Applications After (3)

Application Number Title Priority Date Filing Date
US15/870,401 Active 2031-12-07 US10557020B2 (en) 2011-10-18 2018-01-12 Renewable and cost-effective fillers for polymeric materials
US16/438,874 Abandoned US20190292353A1 (en) 2011-10-18 2019-06-12 Renewable and cost-effective fillers for polymeric materials
US16/438,887 Abandoned US20190292354A1 (en) 2011-10-18 2019-06-12 Renewable and cost-effective fillers for polymeric materials

Country Status (2)

Country Link
US (6) US9902842B2 (en)
SA (1) SA112330644B1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102120870A (en) * 2011-02-28 2011-07-13 殷正福 Degradable plastic and production method thereof
US9347216B2 (en) * 2013-11-21 2016-05-24 United Arab Emirates University Thermal insulation material
CN109354891A (en) * 2018-09-13 2019-02-19 常州厚德再生资源科技有限公司 A kind of PE-PMMA rouge moulding material and preparation method thereof
US10655009B1 (en) 2019-05-13 2020-05-19 United Arab Emirates University Biodegradable composite insulation material
CN110628188B (en) * 2019-09-30 2021-09-07 东莞易昌塑胶布业有限公司 PET composite material prepared by recycling PET plastic waste and application thereof
EP4051729A1 (en) * 2019-10-31 2022-09-07 Dow Global Technologies LLC Article made from post consumer resin with smooth surface finish

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB503180A (en) 1938-09-09 1939-04-03 Hermann Tausig Improvements in mattresses
US2733138A (en) * 1956-01-31 Agricultural residue abrasives
US3539478A (en) * 1968-10-14 1970-11-10 Etablis Organic Products Ground cohune nut shell filler and extender material for thermosetting formaldehyde resin adhesive
US3927235A (en) * 1974-03-18 1975-12-16 Poo Chow Reconstituted board products from plant-fiber residues
US4011130A (en) 1974-09-09 1977-03-08 Minnesota Mining And Manufacturing Company Leather-like waterlaid sheets containing particulate fillers
EP0292628A2 (en) * 1987-05-25 1988-11-30 Panayiotis Stavrakellis Synthetic wood composition from fruit kernels or shells and/or marble chips
US5346930A (en) * 1991-06-13 1994-09-13 Lydall, Inc. Rigid fiberboard
US5951927A (en) * 1996-05-16 1999-09-14 Marley Mouldings Inc. Method of making a polymer and wood flour composite extrusion
US6383053B1 (en) 1999-07-16 2002-05-07 Cherry Hug, Llc Therapeutic products containing cherry pits
JP2005206954A (en) 2004-01-20 2005-08-04 Toyota Boshoku Corp Method for producing interior material
US20050194137A1 (en) * 2004-03-05 2005-09-08 Halliburton Energy Services, Inc. Methods of using partitioned, coated particulates
US20060033229A1 (en) * 2004-07-27 2006-02-16 Daley Scott G Pumice stones and methods for making them
US20070209794A1 (en) * 2006-03-08 2007-09-13 Bj Services Company Curable resin coated low apparent specific gravity beads and method of using the same
US7647964B2 (en) 2005-12-19 2010-01-19 Fairmount Minerals, Ltd. Degradable ball sealers and methods for use in well treatment
US7727940B2 (en) 2006-06-06 2010-06-01 Halliburton Energy Services, Inc. Silicone-tackifier matrixes and methods of use thereof
US20100160505A1 (en) 2005-08-04 2010-06-24 Sadanori Kumazawa Resin composition and molded article made thereof
US7931087B2 (en) 2006-03-08 2011-04-26 Baker Hughes Incorporated Method of fracturing using lightweight polyamide particulates

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2049311A (en) * 1936-07-28 Adhesives and method of making the
US2616862A (en) * 1948-06-25 1952-11-04 Agrashell Inc Phonograph records and molding compositions
BE553961A (en) * 1956-01-06
US3660311A (en) * 1970-01-09 1972-05-02 Int Flavors & Fragrances Inc Novel fragrance methods and compositions
US4849400A (en) * 1988-08-10 1989-07-18 Koch Industries, Inc. Fragrance composition and method
CA2570347A1 (en) 2004-06-14 2005-12-29 Donald J. Vinberg Submersion tank for on-board fish freezing
US20080003430A1 (en) * 2006-06-28 2008-01-03 3M Innovative Properties Company Particulate-loaded polymer fibers and extrusion methods

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2733138A (en) * 1956-01-31 Agricultural residue abrasives
GB503180A (en) 1938-09-09 1939-04-03 Hermann Tausig Improvements in mattresses
US3539478A (en) * 1968-10-14 1970-11-10 Etablis Organic Products Ground cohune nut shell filler and extender material for thermosetting formaldehyde resin adhesive
US3927235A (en) * 1974-03-18 1975-12-16 Poo Chow Reconstituted board products from plant-fiber residues
US4011130A (en) 1974-09-09 1977-03-08 Minnesota Mining And Manufacturing Company Leather-like waterlaid sheets containing particulate fillers
EP0292628A2 (en) * 1987-05-25 1988-11-30 Panayiotis Stavrakellis Synthetic wood composition from fruit kernels or shells and/or marble chips
US5346930A (en) * 1991-06-13 1994-09-13 Lydall, Inc. Rigid fiberboard
US5951927A (en) * 1996-05-16 1999-09-14 Marley Mouldings Inc. Method of making a polymer and wood flour composite extrusion
US6383053B1 (en) 1999-07-16 2002-05-07 Cherry Hug, Llc Therapeutic products containing cherry pits
JP2005206954A (en) 2004-01-20 2005-08-04 Toyota Boshoku Corp Method for producing interior material
US20050194137A1 (en) * 2004-03-05 2005-09-08 Halliburton Energy Services, Inc. Methods of using partitioned, coated particulates
US20060033229A1 (en) * 2004-07-27 2006-02-16 Daley Scott G Pumice stones and methods for making them
US20100160505A1 (en) 2005-08-04 2010-06-24 Sadanori Kumazawa Resin composition and molded article made thereof
US7647964B2 (en) 2005-12-19 2010-01-19 Fairmount Minerals, Ltd. Degradable ball sealers and methods for use in well treatment
US20070209794A1 (en) * 2006-03-08 2007-09-13 Bj Services Company Curable resin coated low apparent specific gravity beads and method of using the same
US7931087B2 (en) 2006-03-08 2011-04-26 Baker Hughes Incorporated Method of fracturing using lightweight polyamide particulates
US7727940B2 (en) 2006-06-06 2010-06-01 Halliburton Energy Services, Inc. Silicone-tackifier matrixes and methods of use thereof

Non-Patent Citations (16)

* Cited by examiner, † Cited by third party
Title
A. Ghazanfari et al.,"Thermal and Mechanical Properties of Blends and Composites from HDPE and Date Pits Particles", Journal of Composite Materials, pp. 77-89, 2008, 42: 77.
Advisory Action for related U.S. Appl. No. 13/275,977 dated Aug. 15, 2013.
Alsewailem, F., et al., "Preparation and characterization of polymer/date pits composites," J. Reinf. Plast. Comp., published online Jun. 23, 2009. *
F.D. Alsewailem et al., "Preparation and Characterization of Polymer/Date Pits Composites", Journal of Reinforced Plastics and Composites, pp. 1743-1749, vol. 29, No. 11/2010.
Final Office Action for related application no. 13/275,977 dated Jun. 6, 2013.
Final Office Action for related U.S. Appl. No. 13/784,067 dated Sep. 24, 2013.
Gregorova, a., et al., "Poly(lactide acid) Composites Reinforced . . . From Different Tissue Types of Picea Sitchensis," J. Applied Polymer Sciences, 2009, 114, pp. 2616-2623.
Notice of Allowance for related U.S. Appl. No. 13/784,067 dated Dec. 24, 2013, 9 pages.
Office Action for related application no. 13/784,067 dated May 9, 2013.
Office Action for related U.S. Appl. No. 13/275,977 dated Sep. 19, 2016, 11 pages.
Oksman, Kristiina, and Craig Clemons. "Mechanical properties polypropylene-wood. " Journal of applied polymer science 67 (1998): 1503-1513.
Stark, N., "Effect of Species and Particle Size on Properties of Wood-Flour-Filled Polypropylene Composites," Functional Fillers, Intertech Conferences, Nov. 1997, pp. 1-22. *
Unknown, "Particle Size - US Sieve Series and Tyler Mesh Size Equivalents. Conversion Table.", Nov. 27, 2006, pp. 1-2.
Van de Velde, K., et al., "Thermoplastic Pultrusion of Natural Fibre Reinforced Composites," Composite Structure, 2001, pp. 355-360.
W. Al-Shahib et al., "The fruit of the date palm . . . the future?", International Journal of Food Sciences and Nutrition, pp. 247-259, vol. 54, Jul. 2003.
Wolf, R., et al., "Plastics, Additives," Ullmann's Encyclopedia of Industrial Chemistry, vol. 27, Jun. 2000, pp. 619-671.

Also Published As

Publication number Publication date
US9902842B2 (en) 2018-02-27
US20130190427A1 (en) 2013-07-25
US20130096238A1 (en) 2013-04-18
US20180134876A1 (en) 2018-05-17
SA112330644B1 (en) 2018-05-02
US20130178562A1 (en) 2013-07-11
US10557020B2 (en) 2020-02-11
US8664300B2 (en) 2014-03-04
US20190292354A1 (en) 2019-09-26
US20190292353A1 (en) 2019-09-26

Similar Documents

Publication Publication Date Title
US10557020B2 (en) Renewable and cost-effective fillers for polymeric materials
Rosa et al. Processing and thermal, mechanical and morphological characterization of post-consumer polyolefins/thermoplastic starch blends
La Mantia et al. Green composites: A brief review
Habibi et al. Processing and characterization of reinforced polyethylene composites made with lignocellulosic fibers from Egyptian agro-industrial residues
Jordá-Vilaplana et al. Development and characterization of a new natural fiber reinforced thermoplastic (NFRP) with Cortaderia selloana (Pampa grass) short fibers
Hamdan et al. Effect of maleated anhydride on mechanical properties of rice husk filler reinforced PLA matrix polymer composite
US10669420B2 (en) Biocarbon and nylon based hybrid carbonaceous biocomposites and methods of making those and using thereof
EP2997079A1 (en) Biomaterial product based on sunflower seed shells and/or sunflower seed hulls
Bashir et al. Recent developments in biocomposites reinforced with natural biofillers from food waste
WO2015039237A1 (en) Hybrid sustainable composites and methods of making and using thereof
KR20130103154A (en) Polypropylene-polylactic acid mixed resin/graphene/natural fiber bionanocomposite and manufacturing method of thereof
Obasi et al. Effect of soil burial on tensile properties of polypropylene/plasticized cassava starch blends
Balart et al. Disintegration in compost conditions and water uptake of green composites from poly (lactic acid) and hazelnut shell flour
Kuram Advances in development of green composites based on natural fibers: A review
Kuram Rheological, mechanical and morphological properties of hybrid hazelnut (Corylus avellana L.)/walnut (Juglans regia L.) shell flour-filled acrylonitrile butadiene styrene composite
Chris-Okafor et al. Reinforcement of high density polyethylene with snail shell powder
Maziero et al. Maleated polypropylene as coupling agent for polypropylene composites reinforced with eucalyptus and Pinus particles
de Almeida Lucas et al. Natural fiber polymer composites technology applied to the recovery and protection of tropical forests allied to the recycling of industrial and urban residues
Obasi et al. Effects of native cassava starch and compatibilizer on biodegradable and tensile properties of polypropylene
Choudhary et al. Bio‐composites from food wastes
Ab Ghani et al. The effects of antioxidants content on mechanical properties and water absorption behaviour of biocomposites prepared by single screw extrusion process
Hatta et al. Mechanical properties of polystyrene/polypropylene reinforced coconut and jute fibers
Ahmad Effect of fiber volume fraction on tensile properties of rice husk reinforced polyester composites
Zaman et al. Preparation and Evaluation of Polypropylene-Peanut Shell Flour Eco-Friendly Composites with and without Cloisite 30B
Chen et al. Characterization of rice husk biofibre-reinforced recycled thermoplastic blend biocomposite

Legal Events

Date Code Title Description
AS Assignment

Owner name: KING ABDULAZIZ CITY FOR SCIENCE AND TECHNOLOGY, SA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ALSEWAILEM, FARES D.;BINKHEDER, YAZEED A.;REEL/FRAME:029927/0794

Effective date: 20130227

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO SMALL (ORIGINAL EVENT CODE: SMAL); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2551); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

Year of fee payment: 4